Dyeing of wool with high-affinity colloidal dyestuffs and di-ammonium phosphate



Patented Apr. 1, 1952 UNITED STATES PATENT OFFICE DYEING i? WOOL WITH HIGH-AFFINITY COLLOIDAL DYESTUFFS AND DI-AMMO- NIUM PHOSPHATE John N. Dalton and JohnP. Ploubides, Lawrence, Mass., assignors to Pacific Mills, Lawrence, Mass, a corporation of Massachusetts No Drawing. Application Noveiiiber 18, 1948, Serial No. 60,833

4 Claims. (01. s-30) 1 The present invention relates to the dyeing of wool with the high afiinity colloidal wool dyes. The high aflinity colloidal wool dyes, due to their high afiinity for W001, produce colors on wool which have excellent fastness to washing and perspiration. However, because of this high affinity for W001, these dyestuffs tend to precipi tate so rapidly on the fiber during the dyeing operation that it has been difficult in commercial practice to obtain level dyeing and even distribution and penetration of color.

The present invention has as an object the provision of dye-baths and dyeing processes for dyeing wool with the high afiinity colloidal wool dyestuffs which will produce dyeings which have excellent fastness to washing and perspiration and which thoroughly penetrate the wool material and are evenly distributed therethrough;

In accordance with the invention we provide an aqueous dye-bath which is distinctly alkaline at the beginning of the treatment and remains distinctly alkaline, as the bath is heated, for a substantial proportion of the process. The distinct alkalinity of our bath in the early stages of the process assures retention of the dyestuff in the bath as a fine dispersion, inhibits fixation of the dye on the wool and promotes swelling of the wool fiber.

This swelling, while the dyestufi remains finely dispersed, facilitates entry of the dyestufi particles into the fiber with the result that the dyestuff thoroughly pentrates the wool material and becomes evenly distributed among and in the fibers before substantial dyeing beings.

With continued heating our dye-bath slowly and uniformly becomes less alkaline until, at

- was about 7.1 at the boil about 6.8, and after2.

the pH values of our dye-bath during heating of the bath.

Tune (M mutes) pH U 7. 15 14:0 7. 83 30 160 7. 85 45 185 7. 78 50 212, 1,; 7- 3O 75 212 I 6- 97 212 I 6. 53 10-5 213 6. 46 212 e 20 212 6. 03 I50 212 5- 78 The following examples are given as illustrations of our invention and not as limitations thereof. The percentages stated in the examples are by weight, based on the weight of the woolto be dyed. The dyestufl? in each instance is mixed with a small amount of water before it is added to the bath.

Example I Ten pieces, totaling six ,hundred pounds, of worsted gabardine cloth which had been previously chrome mordanted were run into a reel type kettle with a water ratio of about 20:01. To this 2% diammonium phosphate is added and the goods allowed to circulate in this medium for 10 minutes. The following dyestuff was then added in the indicated amounts:

Alizarine Grey 2BLW, 0.22%. Pr. 206 Omega Chrome Orange 14%, Sandor Anthraquinone ,Violet 3R,-.03 C. I. 1080 a .Alizarine Brown BL, .40%, Sandoz, Pontachrome Grey GL, .02%, Du Pont Polar Yellow5G, 04%, C. I. 642

The bath was slowly brought to the boil 1 hours) and boiling continued for 2 hours to obtain complete exhaustion. The pH at the start.

hours boil 6.5. The resulting dyeing was well penetrated, level and of good tinctorial value..

Example 11 A dye-bath was prepared as in Example I and 600 pounds of similar chrome mordanted worsted gabardine cloth were dyed with the same dyeing procedure including 2% diammonium phosphate,

, except that after 1 hour boil 1% ammonium sulfate was added, reducing the pH to about 6.5, and after 1 hours boiling time an additional 1% ammonium sulfate was added. The final pH was about 6.3. Chromation and exhaustion is greater by this method than by the method of Example I due to the increased acidity. The resulting dyeing was excellent for penetration, solidity and levelness of color.

Example I 11 Six hundred. pounds of unmordanted worsted gabardine cloth comprising 10 pieces were run into a reel type kettle with a water ratio of about 20:1. To this 5% diammonium phosphate was added to also 1.0% of highly sulfonated castor oil to promote penetration and the goods were allowed to circulate in this medium for minutes. 0.5% sodium bichromate dissolved in a small amount of water was then added, followed by the following dyestuff Alizarine Grey ZBLW, 09%, Pr. 206 Alizarine Brown BL, 075%, Sandoz Eriochrome Flavine A, 06%, C. I. 219 Anthraquinone Violet BR, .05%, C. I. 1080 Omega Chrome Orange ML, 033%, Sandoz The same dyeing time and procedure was ad hered to as in Example II. The resulting dyeing was excellent in penetration, solidity and levelness of color.

- Example IV A 560 lb. lot of unmordanted worsted tropical fabric was entered into a reel type kettle with a water ratio of about :1. To this 6% diammonium phosphate and 0.5% of a highly sulfonated castor oil were added and the goods allowed to circulate in this medium for 10 minutes. The following dissolved dyestuif was then added:

Brilliant Alizarine Bl'ue BS, 1%, sandoz Brilliant Alizarine Mill, Blue BL, 1%, Sandoz Calcocid Alizarine Blue Sky, 0.52%, C. I. 1088 Anthraquinone Violet ER, 13%. C. I. 1080 Polar Yellow 5G, 04%, C. I. 642

Eriochroine- Brown: 3GL, 339%, Geigy Metomega Chrome Brown RRL, .10%, Sandoz Alizarine Grey ZBLW, 01%, Pr. 206 Pontachrome Yellow R, .01 C. I. 343 Anthraquinone Violet3R, 01%, C. I. 1080 The flow of liquor was from inside to outside. The dye-bath was raised to the boil in 1 hour, boiled /g hour and exhausted by the addition of 4 to.6'% of acetic acid of 56% concentration. The dyeing was excellent, with. uniform. color absorption from outside to center.

wool.

Example VI Forty-five pounds of worsted tops (5 lbs. each) were loaded into a Fredericks top dyeing machine with a liquor ratio of about 10:1. 5% diammonium phosphate was added, followed by the following dyestuff combination.

Eriochrome Brown BGL, 39%, Geigy Metomega Chrome Brown REL, .10%, Sandoz Alizarine Gre ZBLW, 01%, Pr. 206 Pontachrome Yellow R, .01%, C. I. 343 Anthraquinone Violet 3R, .01%, C. I. 1080 The flow of liquor was from the inside to the outside. The dye-bath was raised to the boil in 1 hour, boiled hour and exhausted with 2% of acetic acid of 56% concentration. 1% of sodium bichromat-e was added to the bath after exhaustion and boiling continued for 1 hour. The dyeing was excellent, with uniform color absorption from outside to center.

Our process is subject to variation of the conditions described and illustrated in the examples. The process is applicable to wool in any form, such as raw stock, top, slubbing, roving, and woolen or worsted yarn or fabric, and is applicable to the chrome mordant, metachrome or top chrome dyeing processes and to processes inwhich no mordant is employed.

The process also is applicable to all dyestuffs except the acid dyes, and may be used, for example, with dyes of the following classes.

I. Chromate or metachrome dyes, such as:

0. Chrome Brown RLL b Monochrome Black Blue G 0. Chrome Brown BGL II. Neutral or Mil-ling dyes. such as:

a. Polar Red G b. Polar Orange R c. Alizarine Milling Blue BL d. Alizarine Light Brown BL We refer herein to the dyestuffs to which the invention is applicable as the high affinity colloidal wool dyes.

While we prefer to enter the wool into the. dyebath. at room temperatures; as is illustrated in the examples, our process is effective if the wool is entered at any temperature below the. boil.

The amount of diammonium phosphate to be included in the dye-bath may vary from about 0.1% to 0.5% of the total weight of'the bath. which will usually be about 2% to 6% of diammonium phosphate based on the weight ofv the The amount to be use-:1, within this range. can readily be determined by the textile dyer.

The process of the present invention provides dyeings of excellent penetration, levelness and solidity of color on woolen or worsted piece goods, which heretofore have not been completely satisfactorily dyed with the high ailinity colloidal dyes by the existing commercial methods.

We claim:

1. The process for the dyeing of wool with the high affinity colloidal wool dyes which comprises forming distinctly alkaline dye-bath by adding to water a high afiinity colloidal wool dye and an. amount of diammonium phosphate between about 0.1% and 0.5% of the weight of the bath and between about 2% and 6% of the weight of the wool to be dyed, wherein the high affinity colloidal wool dye is present as a dispersion, im mersing the wool in said dye-bath at room temperature, heating the bath slowly below its boil ing temperature for about one to one and one 5. half hours while maintaining the pH of the bath distinctly alkaline, retaining dyestuff in dispersed form in the bath and inhibiting dyestufi fixation on the wool, whereby the wool fiber is swollen and the dyestuff particles are evenly distributed therethrough, and then bringing the bath to the boil and maintaining it at the boil as it becomes distinctly acid by the liberation of ammonia, thus causing fixation of the dyestuff particles on the wool evenly distributed therethrough.

2. The process for the dyeing of chrome mordanted wool with the high afiinity colloidal wool dyes which comprises forming a distinctly alkaline dye-bath by adding to water a mordantable high afiinity colloidal wool dye and an amount of diammonium phosphate between about 0.1% and 0.5% of the weight of the bath and between about 2% and 6% of the weight of the wool to be dyed, wherein the high affinity colloidal Wool dye is present as a dispersion, immersing the wool in said dye-bath at room temperature, heating the bath slowly below its boiling temperature for about one to one and one half hours while maintaining the pH of the bath distinctly alkaline, retaining dyestuflf in dispersed form in the bath and inhibiting dyestuff fixation on the wool, whereby the wool fiber is swollen and the dyestuff particles areevenly distributed therethrough, and then bringing the bath to the boil and maintaining it at the boil as it becomes distinctly acid by the liberation of ammonia, thus causing fixation of the dyestuff particles on the wool evenly distributed therethrough.

3. The process for the dyeing of wool with the high affinity colloidal wool dyes which comprises forming a distinctly alkaline dye-bath by adding to water a mordantable high afiinity colloidal wool dye, a chrome mordant and an amount of diammonium phosphate between about 0.1% and 0.5% of the weight of the bath and between about 2% and 6% of the weight of the wool to be dyed, wherein the high affinity colloidal wool dye is present as a dispersion, immersing the wool in said dye-bath at room temperature, heating the bath slowly below its boiling temperature for about one to one and one half hours while maintaining the pH of the bath distinctly alkaline, retaining dyestuff in dispersed form in the bath and. inhibiting dyestufi fixation on the wool, whereby the wool fiber is swollen and the dyestuff particles are evenly distributed therethrough, and then bringing the bath to the boil and maintaining it at the boil as it becomes distinctly acid by the liberation of ammonia, thus causing fixation of the dyestufi particles on the wool evenly distributed therethrough.

4. The process for the dyeing of wool with the high affinity colloidal wool dyes which comprises forming a distinctly alkaline dye-bath by adding to water a mordantable high afiinity colloidal wool dye and an amount of diammonium phos phate between about 0.1 and 0.5% of the weight of the bath and between about 2% and 6% of the weight of the wool to be dyed, wherein the high afiinity colloidal wool dye is present as a dispersion, immersing the wool in said dye-bath at room temperature, heating the bath slowly below its boiling temperature for about one to one and one half hours while maintaining the pH of the bath distinctly alkaline, retaining dyestufi in dispersed form in the bath and inhibiting dyestufi fixation on the wool, whereby the wool fiber is swollen and the dyestuff particles are evenly distributed therethrough, and then bringing the bath to the boil and maintaining it at the boil as it becomes distinctly acid by the liberation of ammonia, thus causing fixation of the dyestufi particles on the wool evenly distributed therethrough, adding a chrome mordant to the bath and thereafter further boiling the wool in the bath.

JOHN N. DALTON. JOHN P. PLOUBIDES.

REFERENCES CITED The following references are of record in the file of this patent:

FOREIGN PATENTS Country Date Great Britain May 22, 1947 OTHER REFERENCES Number Bird, published in London by Society of Dyers and Colorists, pages 56-63, 1947. Available in Div. 43 of Patent Ofiice. 

1. THE PROCESS FOR THE DYEING OF WOOL WITH THE HIGH AFFINITY COLLOIDAL WOOL DYES WHICH COMPRISES FORMING A DISTINCTLY ALKALINE DYE-BATH BY ADDING TO WATER A HIGH AFFINITY COLLOIDAL WOOL DYE AND AN AMOUNT OF DIAMMONIUM PHOSPHATE BETWEEN ABOUT 0.1% AND 0.5 OF THE WEIGHT OF THE BATH AND BETWEEN ABOUT 2% AND 6% OF THE WEIGHT OF THE WOOL TO BE DYED, WHEREIN THE HIGH AFFINITY COLLOIDAL WOOL DYE IS PRESENT AS A DISPERSION, IMMERSING THE WOOL IN SAID DYE-BATH AT ROOM TEMPERATURE, HEATING THE BATH SLOWLY BELOW ITS BOILING TEMPERATURE FOR ABOUT ONE TO ONE AND ONE HALF HOURS WHILE MAINTAINING THE PH OF THE BATH DISTINCTLY ALKALINE, RETAINING DYESTUFF IN DISPERSED FORM IN THE BATH AND INHIBITING DYESTUFF FIXATION ON THE WOOL, WHEREBY THE WOOL FIBER IS SWOLLEN AND THE DYESTUFF PARTICLES ARE EVENLY DISTRIBUTED THERETHROUGH, AND THEN BRINGING THE BATH TO THE BOIL AND MAINTAINING IT AT THE BOIL AS IT BECOMES DISTINCTLY ACID BY THE LIBERATION OF AMMONIA, THUS CAUSING FIXATION OF THE DYESTUFF PARTICLES ON THE WOOL EVENLY DISTRIBUTED THERETHROUGH. 